KR101460379B1 - Sizing compositions and glass fiber reinforced thermoplastic composites - Google Patents

Abstract

The present invention relates to a sizing composition, glass fiber and glass fiber reinforced composite material at least partially coated with the sizing composition. In one embodiment, the sizing composition comprises the reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with one or more maleic anhydride copolymers, one or more coupling agents, and further an epoxy compound.

Description

[0001] SIZING COMPOSITIONS AND GLASS FIBER REINFORCED THERMOPLASTIC COMPOSITES [0002]

Related application

This application claims priority under 35 USC §119 (e) to U.S. Provisional Patent Application No. 60 / 875,206, filed December 15,2006, which is incorporated herein by reference.

The present invention relates to sizing compositions, glass fibers at least partially coated with a sizing composition, and glass fiber reinforced composite materials.

After formation, the glass fibers are typically treated with a sizing composition capable of imparting the desired properties. As used herein, the terms "sized", "sized", "sizing" and "sizing composition" refer to coating compositions that can be applied to glass fibers after formation of the fibers. The sized glass fibers can be bundled into bundles or strands comprising a plurality of individual fibers after their formation and treatment.

The sizing composition can serve several functions. For example, the sizing composition can act as a lubricant to protect the fibers from abrading each other. The sizing composition can also function to improve the compatibility of the glass fiber and the thermoplastic resin reinforced therewith.

Many glass fiber reinforced thermoplastics are used in the automotive industry. For example, fiberglass-reinforced polyamide resins are often used to fabricate a variety of automotive fluid containers, such as oil pan and radiator parts surrounding the core of a radiator. In recent years, manufacturing techniques for producing thermoplastic resins reinforced with long glass fibers have been developed. Processes such as G-LFT (Granular Long Fiber Technology) and D-LFT (Direct-Long Fiber Technology) reinforce thermoplastic resins with fibers of sufficient length to produce products with desired mechanical properties and durability. However, reinforcing the thermoplastic resin with long glass fibers can lead to several challenges, such as achieving a sufficient wetting of the long fibers with the thermoplastic resin, while ensuring that the length of the glass filaments and the integrity of the thermoplastic resin during the kneading or pultrusion process ), And so on.

Moreover, once a long fiber thermoplastic (LFT) composite has been produced, the specific end use of the composite may entail exposure to harsh physical and chemical conditions that can degrade the composite through a variety of routes. For example, the combination of exposure to aqueous organic solvent mixtures such as ethylene glycol and water and high temperature may reduce the strength of some fiber reinforced polyamide resins.

Summary of the Invention

Some embodiments of the present invention are directed to a sizing composition that can be used to at least partially coat one or more glass fibers. The glass fibers can be further processed in a variety of ways and used in a variety of products, some of which are described herein.

In one embodiment, the sizing composition comprises the reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with one or more maleic anhydride copolymers, one or more coupling agents, and further an epoxy compound.

In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 40% by weight of the sizing composition on a total solids basis. In another embodiment, the reaction product of the alkoxylated amine and the polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 50% by weight of the sizing composition on a total solids basis. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 70% by weight of the sizing composition based on total solids.

In some embodiments, the sizing composition further comprises one or more additional ingredients selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidones, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins or epoxides ≪ / RTI > In some embodiments, the at least one additional component is present in an amount of at least about 1% by weight of the sizing composition based on total solids. In some embodiments, the one or more additional components are present in an amount of at least about 5% by weight of the sizing composition on a total solids basis. In another embodiment, the at least one additional component is present in an amount of up to about 50% by weight of the sizing composition on a total solids basis. Additional embodiments of the sizing composition of the present invention are described below in the Detailed Description section below.

With respect to glass fibers, one embodiment of the present invention includes a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with at least one maleic anhydride copolymer, at least one coupling agent, and further with an epoxy compound Lt; RTI ID = 0.0 > at least < / RTI > In some embodiments, the sizing composition further comprises one or more compounds selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidone, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins or epoxides And further components. Further embodiments of the glass fibers of the present invention are described below in the Detailed Description section. In general, the glass fibers according to various embodiments of the present invention may comprise glass fibers at least partially coated with any of the sizing compositions disclosed herein.

Some embodiments of the present invention relate to glass fiber strands. In one embodiment, the fiberglass strand comprises a plurality of glass fibers, wherein at least one of the plurality of glass fibers is reacted with at least one maleic anhydride copolymer, at least one coupling agent, and further with an epoxy compound At least in part, with a sizing composition comprising a reaction product of an alkoxylated amine and a polycarboxylic acid. In some embodiments, the sizing composition further comprises one or more compounds selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidone, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins or epoxides And further components. Additional embodiments of the glass fiber strands of the present invention are described below in the Detailed Description section below. In general, fiberglass strands according to various embodiments of the present invention can comprise a plurality of glass fibers, wherein at least one of the plurality of glass fibers is at least partially coated with any of the sizing compositions disclosed herein.

Some embodiments of the present invention are directed to roving comprising a plurality of glass fiber strands of the present invention. The roving, in some embodiments, can be assembled by winding a plurality of strands in a single package using a roving winder. In another embodiment, the roving is provided so that a plurality of glass fiber strands are unwound from their respective packages (e.g., a forming package or a direct drawing package) without being wound into a single package, combined into a single roving, So that they can be assembled at the time of use. For example, the roving may be provided in a bath containing thermoplastic resin, chopped, kneaded, or otherwise processed whether rolled into a roving package or assembled at the point of use. The fiberglass strand and roving may be continuous in some embodiments, and in other embodiments may be cut (e.g., chopped) prior to use. Thus, depending on the application, fiberglass strands and glass fiber rovings according to some embodiments of the present invention may have any desired length. Additional embodiments of the roving of the present invention are described below in the Detailed Description section. Generally, the roving may comprise a plurality of strands according to various embodiments of the strands, glass fibers and sizing compositions disclosed herein.

Some embodiments of the present invention are directed to glass fiber reinforced thermoplastic or thermosetting composites. In one embodiment, the glass fiber reinforced thermoplastic or thermosetting composite comprises a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with at least one maleic anhydride copolymer, at least one coupling agent, and further with an epoxy compound At least one glass fiber at least partially coated with a sizing composition comprising a thermoplastic resin or a thermosetting resin. Moreover, any of the sizing compositions described herein as part of the present invention may be used in the composite. For example, in some embodiments of the complex, the sizing composition may further comprise one or more additives selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidone, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins, And one or more additional components including epoxides.

In some embodiments, the thermoplastic resin reinforced with the glass fibers of the present invention comprises a polyolefin such as polyethylenes and polypropylenes, polyamides, polyphenylene oxides, polystyrenes, or polyesters such as polybutylene terephthalate (PBT) Or polyethylene terephthalate (PET), or a combination thereof. In some embodiments, the glass fiber reinforced thermoset resin of the present invention comprises a polyester resin, a polyimide resin, a phenolic resin, a vinyl ester resin, or an epoxy resin, or a combination thereof.

In some embodiments of the fiber reinforced thermoplastic or thermosetting composite, the glass fibers have an average aspect ratio of 50 or greater. As used herein, "aspect ratio" refers to the value (L / D) of the length of the glass fiber divided by the diameter of the glass fiber. The fiber reinforced thermoplastic or thermosetting composite includes a plurality of glass fibers having an average aspect ratio of 100 or more in one embodiment, or an average aspect ratio of 200 or more in another embodiment. In some embodiments, the fiber-reinforced thermoplastic or thermosetting composite comprises a plurality of glass fibers having an average aspect ratio of 500 or more, or in other embodiments, an average aspect ratio of 600 or more. In some embodiments, the fiber reinforced thermoplastic or thermosetting composite comprises a plurality of glass fibers having an average aspect ratio of less than 1500. In another embodiment, the fiber-reinforced thermoplastic or thermosetting composite comprises a plurality of glass fibers having an average aspect ratio of less than 1200, or in other embodiments less than 1000 average aspect ratios. In some embodiments, the fiber reinforced thermoplastic or thermosetting composite comprises a plurality of glass fibers having an average aspect ratio of greater than 1500.

The amount of glass fibers used in some embodiments of the thermoplastic or thermosetting composites of the present invention may also be important. The plurality of glass fibers is present in an amount of at least about 10% by weight of the composite. In some embodiments, the plurality of glass fibers is present in an amount greater than about 40% by weight of the composite. In some embodiments, the plurality of glass fibers is present in an amount greater than about 50% by weight of the composite. In some embodiments, the plurality of glass fibers is present in an amount of up to about 70% by weight of the composite. In some embodiments, the plurality of glass fibers is present in an amount of up to about 90% by weight of the composite. In some embodiments, the plurality of glass fibers have an average aspect ratio consistent with any of the average aspect ratios described herein. In some embodiments, the fiber-reinforced thermoplastic or thermosetting composite comprising the plurality of glass fibers may be in the form of a pellet.

In another aspect, certain embodiments of the present invention are directed to a method of making a glass fiber-reinforced thermoplastic or thermosetting composite. In some embodiments, a method of making a fiber-reinforced thermoplastic or thermosetting composite comprises providing a plurality of continuous phase glass fibers, wherein the plurality of continuous phase glass fibers is mixed with at least one maleic anhydride copolymer, Further comprising at least partially coating with a sizing composition comprising a reaction product of an alkoxylated amine and a polycarboxylic acid, wherein the alkoxylated amine is reacted with an epoxy compound, and positioning the coated plurality of continuous phase glass fibers in a thermoplastic or thermosetting resin . In some embodiments, positioning the coated plurality of continuous phase glass fibers in a thermoplastic or thermosetting resin comprises drawing the coated plurality of continuous phase glass fibers into a thermoplastic or thermosetting resin. Any of the sizing compositions described herein as part of the present invention may be used in the preparation of the composite. For example, in some embodiments, the sizing composition may further comprise one or more additives selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidones, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins or epoxides , ≪ / RTI >

The method of making a fiber-reinforced thermoplastic or thermosetting composite according to some embodiments may further comprise chopping a plurality of continuous phase glass fibers. In some embodiments, the glass fibers can be chopped before being dispersed into the resin. In another embodiment, the glass fibers and the thermoplastic or thermosetting resin can be chopped into pellets (after the glass fibers are dispersed in the resin). In some embodiments, the chopped fibers and / or pellets may have the aspect ratios provided herein. In another embodiment, a method of making a fiber-reinforced thermoplastic or thermosetting composite further comprises molding a plurality of continuous phase glass fibers and a thermoplastic or thermosetting resin. Additional embodiments for making fiber-reinforced thermoplastic or thermosetting composites are described below in the Detailed Description section.

While some embodiments of the method according to the present invention relate to glass fibers, those of ordinary skill in the art will understand that the glass fibers may be in the form of strands, rovings comprising a plurality of strands, and other glass fiber products . These and other embodiments are described in more detail in the following detailed description.

It is to be understood that for purposes of this specification, all numbers expressing quantities of ingredients, reaction conditions, and the like used herein are to be understood as being adjusted to the term "about" in all cases. Accordingly, unless otherwise stated, the numerical values set forth in the following specification are approximations that may vary depending upon the desired properties of the present invention. At the very least, and without wishing to restrict the application of the doctrine of equivalents, each numerical parameter should at least be understood by applying ordinary approximation techniques in light of the numerical values reported.

Although numerical ranges and variables describing the broad scope of the invention are approximations, the numerical values set forth in the specific examples are described as precisely as possible. However, any numerical value inherently contains certain errors caused by the standard errors found in their respective test measurements.

It is also to be understood that the singular forms as used herein include the plural unless it is explicitly stated or explicitly limited.

In some embodiments, the sizing composition of the present invention comprises a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with one or more maleic anhydride copolymers, one or more coupling agents, and further an epoxy compound.

In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 40% by weight of the sizing composition on a total solids basis. In another embodiment, the reaction product of the alkoxylated amine and the polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 50% by weight of the sizing composition on a total solids basis. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 70% by weight of the sizing composition based on total solids.

In some embodiments, the sizing composition further comprises one or more additional ingredients selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidones, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins or epoxides ≪ / RTI >

Returning to components that may be included in various embodiments of the sizing composition of the present invention, the sizing composition of the present invention may comprise one or more maleic anhydride copolymers. In some embodiments, the maleic anhydride copolymer comprises a maleic anhydride monomer and a monomer selected from the group consisting of ethylene, butadiene, isobutylene, and mixtures thereof. In another embodiment, the maleic anhydride copolymer comprises a maleic anhydride monomer and a monomer selected from the group consisting of ethylene, butadiene, and mixtures thereof. In a further embodiment, the maleic anhydride copolymer comprises maleic anhydride monomer and isobutylene.

In some embodiments, the maleic anhydride copolymer comprises a maleic anhydride monomer and a copolymerizable monomer, wherein a portion of the maleic anhydride copolymer is chemically modified with ammonia or a primary alkyl amine. In another embodiment, the maleic anhydride copolymer comprises a maleic anhydride monomer and a copolymerizable monomer, wherein a portion of the maleic anhydride copolymer is chemically modified with ammonia. In another embodiment, the maleic anhydride copolymer comprises a maleic anhydride monomer and a copolymerizable monomer, wherein the maleic anhydride copolymer is chemically modified with a primary alkyl amine. In addition, chemically modifying a portion of the maleic anhydride copolymer with ammonia can convert the maleic anhydride monomer to a maleimide monomer. Chemically modifying a portion of the maleic anhydride copolymer with a primary alkyl amine can convert the maleic anhydride monomer to an alkyl substituted maleimide monomer.

In another embodiment, the maleic anhydride copolymer comprises a maleic anhydride monomer, a copolymerizable monomer, and a monomer selected from the group consisting of maleimide monomers, alkyl substituted maleimide monomers, and mixtures thereof. In some embodiments, the maleic anhydride copolymer includes a maleic anhydride monomer, a copolymerizable monomer, and a maleimide monomer. In another embodiment, the maleic anhydride copolymer comprises a maleic anhydride monomer, a copolymerizable monomer, and an alkyl substituted maleimide monomer.

The term "maleic anhydride monomer" as used herein includes maleic anhydride and the free acid, salt or partial salt form of maleic acid. As used herein, the term " partial salt "refers to a maleic anhydride monomer having two carboxy groups, one carboxy group being in the free acid form and the other carboxy group being converted into the salt. The term "maleimide monomer" as used herein includes the free acid or salt forms of maleimide, maleic diamide and maleic acid amide. The term " alkyl substituted maleimide monomer "as used herein includes the free acid or salt forms of N-alkyl maleimide, N, N'-dialkyl maleate diamide and N-alkyl maleic acid amide.

In some embodiments, the maleic anhydride copolymer is formed from polymerizing maleic anhydride or maleic acid with copolymerizable monomers such as, but not limited to, ethylene, butadiene, isobutylene, and isobutylene. As noted above, in some embodiments, the maleic anhydride copolymer comprises a maleic anhydride monomer, a copolymerizable monomer, and a monomer selected from the group consisting of maleimide monomers, alkyl substituted maleimide monomers, and mixtures thereof And may include a terpolymer. The ratio of the monomers in the maleic anhydride copolymer is not particularly limited as long as the maleic anhydride copolymer functions to maintain or improve the hydrolysis resistance and / or strength of the reinforced thermoplastic resin. When the maleic anhydride copolymer is formed from a reaction mixture comprising monomers copolymerizable with maleic anhydride, the resulting maleic anhydride copolymer can in many cases be an alternating copolymer of the two reactants. Additional chemical modification of the alternating maleic anhydride copolymer produces maleic anhydride copolymers with a 1: 1 ratio of maleic anhydride, maleimide and N-substituted maleimide monomer to copolymerizable monomer in some cases.

An aqueous solution of the maleic anhydride copolymer may be used when formulating some embodiments of the sizing composition of the present invention. In the case of a maleic anhydride copolymer having maleic anhydride monomer in an anhydrous form, the maleic anhydride copolymer may not be well dissolved when dispersed in water at room temperature. The solubility of the maleic anhydride copolymer can be improved by heating an aqueous solution of the maleic anhydride copolymer and converting the anhydride group of the maleic anhydride copolymer to the corresponding polyacid. An aqueous solution formed by hydrolysis can then be used to formulate the sizing composition.

Upon hydrolysis, the free acid group of the maleic anhydride copolymer may be further converted to a salt in the free acid. In another method of preparing an aqueous solution of the maleic anhydride copolymer, the maleic anhydride copolymer having the maleic anhydride monomer in the anhydrous form can be heated in aqueous ammonium hydroxide solution or aqueous primary alkylamine solution. The reaction mixture can be heated to a temperature above 100 < 0 > C under pressure. Depending on the reaction conditions and the presence of ammonium hydroxide or primary alkylamine, some or all of the anhydride groups may be converted to polyacids, salts, partial salts, diamides, partial amides, imides, and mixtures thereof.

In some embodiments, the formation of diamides, partial amides and imides in the maleic anhydride copolymer imparts properties favorable to fiber-reinforced polyamides. The formation of these functional groups can provide an affinity for the maleic anhydride copolymer to react with the amine-terminal group of the polyamide resin through a transamidation reaction mechanism.

The salt of hydrolyzed maleic anhydride may also be an alkali metal or ammonium salt derived from ammonium hydroxide or poly- or mono-functionalized organic primary, secondary or tertiary amines (e.g. triethylamine and triethanolamine) have. The degree of neutralization of the hydrolyzed maleic anhydride may vary. In one embodiment, the maleic anhydride copolymer is neutralized with a 25% aqueous ammonium hydroxide solution.

As used herein, "copolymerizable monomer" refers to a material that can be copolymerized with maleic anhydride and includes, but is not limited to, aliphatic olefins, vinyl ethers, vinyl acetate and other vinyl type monomers. The copolymerizable aliphatic olefin is of the formula:

Wherein R ¹ and R ² are each independently selected from the group consisting of hydrogen, alkyl and alkenyl groups having from 1 to 12 carbon atoms.

Examples of suitable aliphatic olefins to be copolymerized with maleic anhydride include ethylene, butadiene and isobutylene. An example of a vinyl ether suitable for copolymerization with maleic anhydride is isobutylene.

The amount and type of maleimide monomer or N-substituted maleimide monomer in the maleic anhydride copolymer is, in some embodiments, selected from the group consisting of the maleic anhydride copolymer and a particular thermoplastic resin, such as a polyamide resin, Such as the desired viscosity of the composition. The greater number of amide or imide groups in the maleic anhydride copolymer can reduce the solubility of the maleic anhydride copolymer in aqueous solution. Acids, such as esters, may not provide acceptable reactivity with polyamide resins, as compared to amides, imides, anhydrides, free acids and salts.

In one embodiment, the maleic anhydride copolymer is an alternating copolymer of maleic anhydride monomer and ethylene. Alternating copolymers of maleic anhydride and ethylene can be obtained from Zeeland Chemicals, Inc. In another embodiment, the maleic anhydride copolymer is an alternating copolymer of maleic anhydride monomer and butadiene. An alternating copolymer of maleic anhydride and butadiene, known as MALDENE 286, may be obtained from Lindau Chemicals, Inc. In another embodiment, the maleic anhydride copolymer is an alternating copolymer of maleic anhydride monomer and isobutylene. In another embodiment, the maleic anhydride copolymer is an alternating copolymer of maleic anhydride monomer and ethylene. An alternating copolymer of maleic anhydride monomer and isobutylene, known as IREZ 160, can be obtained.

The amount of maleic anhydride copolymer in the sizing composition may depend on various factors. In some embodiments, the lower limit of the maleic anhydride copolymer can be determined in an amount effective to maintain or improve the hydrolytic resistance of the enhanced thermoplastic resin. In one embodiment where the sized glass fiber is intended for use in reinforcing thermoplastic polyamide resins, for example, the amount of maleic anhydride copolymer in the sizing composition effective to maintain or improve the hydrolytic resistance of the thermoplastic polyamide resin, By weight to 1% by weight. In some polyamide reinforced embodiments, the lower limit of the maleic anhydride copolymer may also be determined to a minimum amount suitable to provide suitable reactivity with the polyamide resin. In some embodiments, the maleic anhydride copolymer may be present in an amount greater than 10 weight percent based on total solids. Moreover, the upper limit of the maleic anhydride copolymer may be less than 50% by weight based on total solids in some embodiments. In some embodiments, the amount of maleic anhydride copolymer in the sizing composition may range from about 5 to 25 weight percent based on total solids. In some embodiments, the maleic anhydride copolymer is present in an amount of up to about 40% by weight of the sizing composition based on total solids.

In some embodiments, the sizing composition of the present invention comprises a polymer or oligomer comprising a plurality of acid functional groups, e.g., carboxylic acid functional groups, instead of the maleic anhydride copolymer. In one embodiment, the polymer or oligomer comprising a plurality of acid functional groups is at least one of acrylic, e.g., polyacrylic acid (PAA), polymethacrylic acid (PMA), polymethylmethacrylate (PMMA) . In some embodiments, the acrylic system comprises a copolymer of acrylic monomers (e.g., acrylic acid, methacrylic acid, and methyl methacrylate) and styrene. The acrylic / styrene copolymer comprises at least 5% by weight of acrylic system in one embodiment. In another embodiment, the acrylic / styrene copolymer comprises from 10% to 50% acrylic by weight.

In some embodiments, the polymer or oligomer comprising a plurality of acid functional groups suitable for replacing the maleic anhydride copolymer is present in an amount of at least 5% by weight of the sizing composition based on total solids. In another embodiment, the polymer or oligomer comprising a plurality of acid functional groups is present in an amount of at least 10% by weight of the sizing composition on a total solids basis. In some embodiments, the polymer or oligomer comprising a plurality of acid functional groups suitable for replacing the maleic anhydride copolymer is present in an amount of less than 30% by weight of the sizing composition on a total solids basis. In some embodiments, the polymer or oligomer comprising a plurality of acid functional groups is present in an amount less than 20% by weight of the sizing composition on a total solids basis.

Some embodiments of the sizing composition of the present invention additionally comprise at least one cuffing agent. The silane coupling agent useful in the sizing composition of the present invention comprises a functional group capable of chemically bonding to the surface of the glass fiber and a second functional group capable of chemically bonding to the resin. Thus, the specific silane coupling agent included in the sizing composition can be determined by a resin using glass fibers sized to enhance it. Two or more coupling agents may be used together. Silane coupling agents useful in some embodiments of the present invention may include aminosilanes. Examples of aminosilanes that may be useful in embodiments of the amide resin-reinforcing sizing composition include aminosilanes such as aminopropyltrialkyloxysilanes such as gamma -aminopropyltrimethoxysilane, gamma -aminopropyltriethoxysilane, and N aminopropyltrimethoxysilane, N-beta (aminoethyl) gamma -aminopropyltrimethoxysilane and N-beta (aminoethyl) gamma -aminopropyltriethoxysilane. Aminosilane. ≪ / RTI > In one embodiment where the sized glass fibers are used to reinforce the polyamide resin, the coupling agent is commercially available from? -Aminopropyltriethoxysilane, for example, Degussa AG, Commercially available A-1100 from DYNASYLAN AMEO and available from Osi Specialties, Terrytown, New York, USA. For example, based on the resin to be reinforced by the sized fibers, other silane coupling agents may be used. For example, in embodiments where the polyethylene or polybutylene terephthalate thermoplastic resin is reinforced, a suitable coupling agent may, in some embodiments, comprise an epoxy silane.

The amount of coupling agent in the sizing composition may depend on a variety of factors such as, for example, the affinity of the coupling agent for a particular resin and compatibility of the coupling agent with other sizing composition components. In some embodiments, the coupling agent may be present in an amount up to about 10% by weight in the sizing composition on a total solids basis. In some embodiments, the coupling agent may be present in an amount up to about 20 weight percent in the sizing composition on a total solids basis. In another embodiment, the coupling agent may be present in an amount greater than about 2 weight percent based on total solids. In some embodiments, the coupling agent may be present in an amount greater than about 4 weight percent based on total solids. In some embodiments, the coupling agent may be present in an amount of up to about 15 weight percent based on total solids. In some embodiments, the coupling agent may be present in an amount of less than about 7% by weight based on total solids. In a further embodiment wherein the coupling agent comprises gamma -aminopropyltriethoxysilane, the amount of coupling agent may range from 2 to 7 wt% based on total solids.

In some embodiments, the sizing composition of the present invention also comprises the reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound. In some embodiments, the reaction product is present in an amount greater than about 40% by weight of the sizing composition on a total solids basis. In another embodiment, the reaction product of the alkoxylated amine and the polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 50% by weight of the sizing composition on a total solids basis. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 70% by weight of the sizing composition based on total solids.

The reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound, in some embodiments, includes the reaction product disclosed in U.S. Patent No. 3,459,585, the entire contents of which are incorporated herein by reference. In some embodiments, the alkoxylated amine for reaction with the polycarboxylic acid has the formula:

In this formula,

R is selected from the group consisting of hydrogen, saturated or unsaturated alkyl containing from 1 to 30 carbon atoms, aryl, arylalkyl and alkylaryl radicals,

In some embodiments, x and y are independently in the range of 1 to 100.

In some embodiments, x and y independently range from 20 to 50. In some embodiments, In another embodiment, x and y are independently in the range of 30 to 60.

In another embodiment, the alkoxylated amine for reaction with the polycarboxylic acid has the formula:

In this formula,

R ¹ and R ² are independently selected from the group consisting of hydrogen, saturated or unsaturated alkyl, aryl, arylalkyl and alkylaryl radicals containing from 1 to 30 carbon atoms,

In some embodiments, x ranges from 1 to 100.

In some embodiments, x ranges from 20 to 50. In another embodiment, x ranges from 30 to 60.

In some embodiments, the alkoxylated amine for reaction with the polycarboxylic acid comprises an alkoxylated aliphatic amine. In some embodiments, for example, the alkoxylated aliphatic amine is an alkoxylated stearylamine, an alkoxylated dodecylamine, an alkoxylated tetradecylamine, an alkoxylated hexadecylamine, or an alkoxylated octadecylamine. .

In some embodiments, the alkoxylated amine for reaction with the polycarboxylic acid comprises a propoxylated amine or a butoxylated amine. Embodiments of the sizing compositions of the present invention can be any of the carbon atoms in the alkoxy moiety of the alkoxylated amine (e.g., ethoxy, propoxy, butoxy, pentoxy, etc.) that provide the desired properties described herein to the sizing composition . In some embodiments, the molecular weight of the alkoxylated amine for reaction with the polycarboxylic acid may range from about 100 to about 10,000.

In some embodiments, alkoxylated amides can be used in place of alkoxylated amines in the preparation of the reaction products used in the sizing compositions of the present invention. In some embodiments, the alkoxylated amide may have the formula:

In this formula,

R ³ is selected from the group consisting of saturated or unsaturated alkyl, aryl, arylalkyl and alkylaryl radicals containing 1 to 30 carbon atoms,

x and y are independently in the range of 1 to 100.

In some embodiments, x and y independently range from 20 to 50. In some embodiments, In another embodiment, x and y are independently in the range of 30 to 60.

In another embodiment, the alkoxylated amide for reaction with the polycarboxylic acid has the formula:

In this formula,

R ⁴ and R ⁵ are independently selected from the group consisting of hydrogen, saturated or unsaturated alkyl, aryl, arylalkyl and alkylaryl radicals containing from 1 to 30 carbon atoms,

x ranges from 1 to 100.

In some embodiments, x ranges from 20 to 50. In some embodiments, x ranges from 30 to 60.

In some embodiments, the alkoxylated amide for reaction with the polycarboxylic acid comprises a propoxylated amide or a butoxylated amide. Embodiments of the sizing compositions of the present invention can be any of the carbon atoms in the alkoxy moiety of the alkoxylated amide (e.g., ethoxy, propoxy, butoxy, pentoxy, etc.) that provide the desired properties described herein to the sizing composition . In some embodiments, the molecular weight of the alkoxylated amide for reaction with the polycarboxylic acid may range from about 100 to about 10,000.

Suitable polycarboxylic acids for reaction with alkoxylated amines or alkoxylated amides include, in some embodiments, oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, But are not limited to, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, muconic acid, 1,2-cyclohexanedicarboxylic acid, 1,4- cyclohexanedicarboxylic acid, malic acid, tartaric acid, phthalic acid, isophthalic acid, terephthalic acid, , Tetrachlorophthalic acid, tricarbalic acid and the corresponding acid anhydrides of the above acids.

Suitable epoxy compounds for further reaction with the reaction product of an alkoxylated amine or alkoxylated amide and a polycarboxylic acid include species having at least one epoxy moiety of the following general formula (6).

Such epoxy compounds are well known in the art and, in some embodiments, may be polymeric or oligomeric. In one embodiment, the epoxy compound comprises a polyepoxide compound, such as diglycidyl ether, diglycidyl ester, or mixtures thereof. In some embodiments, diglycidyl ethers include alkyl or aromatic diglycidyl ethers. In some embodiments, the diglycidyl ester comprises an alkyl or aromatic diglycidyl ester.

In some embodiments, the reaction product of the alkoxylated amine and the polycarboxylic acid, which is further reacted with the epoxy compound, can be produced by reacting 1 mole of the primary alkoxylated amine of Formula 2 and 2 moles of the polycarboxylic acid. The resulting reaction intermediate is then reacted with 2 moles of epoxy compound. Without wishing to be bound by any theory, it is believed that, in the reaction mechanism, one carboxyl group of each mole of the polycarboxylic acid is esterified into one terminal hydroxyl group of the alkoxylated primary amine, It is believed to be left behind. Each of the available carboxyl groups is then esterified by reaction with the epoxy group of the epoxy compound. In some embodiments in which the polyepoxide compound is used, the resulting reaction product may have an epoxy group available for further reaction.

In one embodiment, for example, one mole of an alkoxylated primary amine is reacted with two moles of polycarboxylic acid derived from phthalic anhydride to yield an intermediate of formula (7) wherein the number of carboxyl groups available for further reaction is two.

The intermediate of formula (7) is then reacted with 2 moles of bisphenol A diglycidyl ether having an epoxide equivalent of 186 to 189. The available carboxyl groups in the intermediate of formula (7) are each esterified by reaction with an epoxy group of bisphenol A diglycidyl ether to yield a reaction product of formula (8).

The reaction product of Formula 8 may be incorporated into the sizing composition according to some embodiments of the present invention.

In some embodiments, the reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound, can be produced by reacting 1 mole of the alkoxylated amine of Formula 3 with 1 mole of polycarboxylic acid. The resulting intermediate product is then reacted with the die epoxy compound in a molar ratio of intermediate product to die epoxy compound of 2: 1. Without wishing to be bound by any theory, it is believed that in the reaction mechanism, one carboxyl group of the polycarboxylic acid is esterified to the terminal hydroxyl group of the alkoxylated secondary amine, leaving one or more carboxyl groups available for further reaction do. The available carboxyl groups are then esterified by reaction with the epoxy group of the epoxy compound.

In one embodiment, for example, one mole of an alkoxylated secondary amine reacts with one mole of a polycarboxylic acid derived from phthalic anhydride to yield an intermediate with one carboxyl group available for further reaction. The intermediate is then reacted with a bisphenol A diglycidyl ether having an epoxide equivalent of 186 to 189 in a 2: 1 molar ratio. Each epoxy group of the bisphenol A diglycidyl ether is then esterified by the free carboxyl group of the intermediate to yield the reaction product of formula (9).

The reaction product of Formula 9 may be incorporated into a sizing composition according to some embodiments of the present invention.

Further reaction products of alkoxylated amines and polycarboxylic acids, which are further reacted with epoxy compounds, suitable for use in some embodiments of the sizing compositions of the present invention are commercially available from Hexion Specialty Chemicals as RD1135- B can be purchased.

In some embodiments, the sizing composition of the present invention may further comprise at least one of chemically modified rosin, polyvinyl alcohol, acrylic, polyurethane, polyester, epoxide, polyvinylpyrrolidone, fatty acid esters of polyethylene glycol, And < / RTI > In some embodiments, the one or more additional components are present in an amount of at least about 1% by weight of the sizing composition on a total solids basis. In some embodiments, the one or more additional components are present in an amount of at least about 5% by weight of the sizing composition on a total solids basis. In another embodiment, the at least one additional component is present in an amount of up to about 50% by weight of the sizing composition on a total solids basis.

Chemically modified rosins suitable for use in the sizing compositions of the present invention include, in some embodiments, the chemically modified rosins disclosed in U.S. Patent Application No. 11 / 386,898, which is incorporated herein by reference in its entirety . In some embodiments, the chemically modified rosin suitable for use in the sizing composition of the present invention has the structure of Formula 10:

In this formula,

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are the same or different and independently represent hydrogen, alkyl, alkenyl, alkynyl (COOH) and alkenyl- (COOH), in the presence of a base, such as an alkoxyl, an alkoxyl, a thioalkyl, an amine, an alkylamine, an alkenylamine, a hydroxyl, an alkyl-OH,

In another embodiment, the chemically modified rosin that may be used in some embodiments of the sizing composition of the present invention includes DYNAKOLL Si 100, commercially available from Eka Chemicals AB, Sweden do.

The one or more additional components according to some embodiments may comprise polyvinyl alcohol. Suitable polyvinyl alcohols for use in some embodiments of the sizing compositions of the present invention may include polyvinyl alcohol derived from polyvinyl acetate by a hydrolysis or saponification process. Various grades of polyvinyl alcohol are available and are often distinguished by their degree of hydrolysis and viscosity. The sources of polyvinyl alcohol typically characterize their polyvinyl alcohol products on the basis of the degree of hydrolysis, and the term "degree of hydrolysis" herein has the same meaning as understood by those of ordinary skill in the art .

Polyvinyl alcohol may be characterized herein in terms of the degree of hydrolysis. In some embodiments, the polyvinyl alcohol for use in the sizing composition of the present invention may be more than 80% hydrolyzed. In another embodiment, the polyvinyl alcohol may be more than 85% hydrolyzed. In another embodiment, the polyvinyl alcohol may be more than 98% hydrolyzed.

According to some embodiments of the present invention, the polyvinyl alcohol may comprise polyvinyl alcohol having a certain average degree of hydrolysis. According to another embodiment, the polyvinyl alcohol may comprise a mixture of polyvinyl alcohols having different average degree of hydrolysis. In one embodiment, for example, the polyvinyl alcohol component in the sizing composition may comprise a mixture of greater than 85% hydrolyzed polyvinyl alcohol and greater than 98% hydrolyzed polyvinyl alcohol. Embodiments of the present invention include mixtures of any combination of polyvinyl alcohols.

Non-limiting examples of commercially available polyvinyl alcohols that may be used in some embodiments of the sizing compositions of the present invention include polyvinyl alcohols of the CELVOL (R) series, available from Celanese Corporation can do. Some examples of CELVOL (R) series polyvinyl alcohols that can be used in various embodiments of the sizing compositions of the present invention are provided in Table 1 below.

Polyvinyl alcohol Hydrolysis% Viscosity mPa (4% / 20 캜) Cellol (R) 205 88 5.7 Cellol (registered trademark) 203 88 4.0 Cellol (registered trademark) 502 88 3.4 Cellol (registered trademark) 305 98.4 5.0 Cellol (registered trademark) 103 98.4 4.0

Additional non-limiting examples of commercially available polyvinyl alcohols that may be used in some embodiments of the sizing compositions of the present invention include the MOWIOL (R) series of commercially available polyvinyl alcohols available from Kuraray Specialties Europe Polyvinyl alcohol. Some examples of the MOWIOL (R) series of polyvinyl alcohols that can be used in various embodiments of the sizing compositions of the present invention are shown in Table 2 below.

Polyvinyl alcohol Hydrolysis% Viscosity mPa (4% / 20 캜) MoIyol (R) 4-88 87.7 4.0 Mowiol (R) 3-83 82.6 3.0 Mowiol (R) 3-98 98.4 3.5

In some embodiments of the sizing composition of the present invention, the one or more additional components may comprise acrylic and derivatives thereof. In some embodiments, the acrylic system can include monomeric, oligomeric and polymeric forms of acrylic acid and methacrylic acid and their esters, acrylonitrile, and acrylamide. For example, in one embodiment, the acrylic system may comprise methacrylate and methyl methacrylate monomers. In another embodiment, the acrylic system may comprise oligomers and polymers having at least one acrylic acid moiety, such as polyacrylic acid (PAA), polymethacrylic acid (PMA) and polymethylmethacrylate (PMMA) have. In some embodiments, the acrylic acid moiety may be incorporated into the backbone of the oligomer or polymer, or alternatively it may be a substituent attached to the backbone.

In some embodiments, the one or more additional components of the sizing composition of the present invention may comprise a polyurethane. In some embodiments, the polyurethane is an aqueous dispersion of a polyurethane, such as WITCOBOND W-290H commercially available from Crompton Corporation-Uniroyal Chemical and WitcoBond W -296, available from Reichhold Chemical Company, and Aquathane 516 available from Reichhold Chemical Company. Other suitable aqueous polyurethane dispersions include Hydrosize U2-01, commercially available from Hydrosize Technologies, Inc. of Raleigh, North Carolina.

Other embodiments in which the thermoplastic polyamide resin is reinforced include by reaction between various polyurethane dispersions such as organic isocyanates or polyisocyanates and organic polyhydroxylated compounds or hydroxyl terminated polyether or polyester polymers The resulting aqueous polyurethane polymer solution may be useful. The polyurethane dispersion may contain a crosslinking group. Another example of a suitable polyurethane is the aqueous emulsion of polyether-polyurethane NAJ-1037 from Bayer Chemical. The polyurethane may also be part of a dispersion comprising an isocyanate blocked with polyurethane. For example, the following polyurethane / blocked isocyanate emulsions may be suitable for use in the sizing compositions of the present invention: Whitcomb 60X (Crompton), Baybond 403 (Bayer), Baybond PU-130 Nexco D641 (Henkel), Neoxil 6158 (DSM), and Vestanat EP-DS-1205 (Degussa).

In some embodiments, the at least one additional component comprises a blocked isocyanate. The term " blocked isocyanate ", as used herein, refers to an isocyanate group in which the isocyanate group has been reacted with the compound such that the resulting blocked isocyanate is stable to active hydrogen at 25 < 0 > C and at a temperature below any film- Quot; refers to any isocyanate that is reactive with active hydrogens in the process. Two or more blocked isocyanates may be used together.

Any suitable organic polyisocyanate can be used to prepare the blocked organic isocyanate. Suitable organic polyisocyanates include, for example, but not limited to, the ability of the polyisocyanate to interact with the thermoplastic resin during drying and extrusion of the sizing composition and / or the ability of the polyisocyanate to interact with the maleic anhydride copolymer Lt; / RTI > Representative examples of organic polyisocyanates which may be suitable organic polyisocyanates include aliphatic compounds such as those required for the formation of trimethylene, tetramethylene, hexamethylene and butyrylidenediisocyanate, or isophorone diisocyanate (IPDI); Cycloalkylene compounds such as 1,4-cyclohexane diisocyanate; aromatic compounds such as p-phenylene diisocyanate; 4,4'-diphenylene methane diisocyanate, aliphatic-aromatic compounds such as 2,4- or 2,6-tolylene diisocyanate, or mixtures thereof. Representative examples of higher-grade polyisocyanates include triisocyanates such as triphenylmethane-4,4 ', 4 "-triisocyanate and 2,4,6-triisocyanate toluene. The organic polyisocyanates Additional examples of biuret types include those that produce a 4-, 5-, or 6-membered ring in a dimerization or trimerization reaction. As the 6-membered ring, various diisocyanates alone, or Isocyanuric rings derived from other isocyanate (s) (e.g., mono-, di- or polyisocyanate (s)) or homo- or hetero-trimerization with carbon dioxide. When carbon dioxide is used, The nitrogen of the cyanuric ring is replaced by oxygen.

The one or more additional components of the sizing composition of the present invention, in some embodiments, may comprise a polyester. Polyesters suitable for use in some embodiments of the sizing compositions of the present invention may include saturated and / or unsaturated linear polyesters. In another embodiment, suitable polyesters may include cross-linked polyesters such as alkyd polyesters. In some embodiments, the polyester may have a molecular weight of less than about 5000. In some embodiments, the polyester for use in the sizing composition of the present invention comprises adipic acid polyester, such as Desmophene polyester, commercially available from Bayer AG. In another embodiment, the polyester for use in the sizing composition of the present invention may comprise a bisphenol A polyester such as tetrasiloxane 954D, commercially available from DSM, B. V., Netherlands.

In some embodiments, the one or more additional components of the sizing composition of the present invention may comprise an epoxide. Suitable epoxides according to some embodiments include EPON epoxide and EPI-REZ epoxide commercially available from Miller-Stephenson Products. In some embodiments, suitable epoxides may include low molecular weight polyester epoxides and / or low molecular weight polyurethane epoxides.

In some embodiments, the one or more additional components may comprise polyvinylpyrrolidone. An example of a suitable polyvinylpyrrolidone for use in the sizing composition of the present invention is, in some embodiments, commercially available under the trade name PVP K-30 from GAF Corporation. In some embodiments, suitable polyvinylpyrrolidones may also include Sokolan CP45, Sowolan CP9, and Sowolan CP13S from BASF.

In a further embodiment, the one or more additional ingredients may comprise a fatty acid ester of polyethylene glycol (PEG). In some embodiments, the fatty acid ester may comprise a polyethylene glycol and a diester of tallic acid. One example of a suitable polyethylene glycol and deacidified diester is commercially available under the trade name MAPEG-600-DOT from BASF Corporation.

In some embodiments, the sizing composition of the present invention comprises at least one maleic anhydride copolymer, at least one coupling agent, and at least one polymer selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidones, fatty acid esters of polyethylene glycols, , A chemically modified rosin, or an epoxide. Each of these components has been described above in connection with the above embodiments in which these components are used in conjunction with the reaction product of an alkoxylated amine and a polycarboxylic acid that is further reacted with an epoxy compound.

In some embodiments, the one or more additional components are present in an amount of at least about 40% by weight of the sizing composition on a total solids basis. In another embodiment, the one or more additional components are present in an amount of at least about 50% by weight of the sizing composition on a total solids basis. In some embodiments, the one or more additional components are present in an amount greater than about 70% by weight of the sizing composition on a total solids basis. Also, in some embodiments, the one or more maleic anhydride copolymers and the one or more coupling agents may be present in any amount consistent with those set forth above for other embodiments.

In another aspect, some embodiments of the present invention relate to glass fibers that are at least partially coated with any of the sizing compositions described herein. For example, in some embodiments, the glass fibers comprise a sizing agent comprising a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with at least one maleic anhydride copolymer, at least one coupling agent, And may be at least partially coated with a composition. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 40% by weight of the sizing composition on a total solids basis. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 70% by weight based on total solids.

In some embodiments, the sizing composition for at least partially coating the glass fibers may further comprise one or more additives selected from the group consisting of polyester, polyvinyl alcohol, polyurethane, polyvinylpyrrolidone, fatty acid esters of polyethylene glycol, acrylic, wax, chemically modified Rosin, or an epoxide.

The type of glass fiber to be sized can be determined by a variety of factors such as, for example, the intended end use of the sized glass fiber, but is not limited thereto. For example, the glass fibers may be of any type compatible with the thermoplastic resin to which the glass fibers are to be reinforced.

In some embodiments, the average diameter of the glass fibers may be greater than 8 microns. In another embodiment, the average diameter of the glass fibers may be less than 25 占 퐉. The choice of the nominal diameter of the glass fibers according to embodiments of the present invention may depend on many factors, including the amount of glass desired in the final product, the strength of the desired glass, the diameter of the glass fibers primarily made in a particular location,

Non-limiting examples of glass fibers suitable for use in the present invention include "E-glass", "A-glass", "C-glass", "S- glass", "ECR- And those made from fibrous glass compositions such as fluorine- and / or boron-free derivatives thereof. A typical formulation of glass fiber is described in K. Lowenstein, The Manufacturing Technology of Continuous Glass Fibers , (3 ^rd Ed. 1993).

The sizing composition of the present invention can be prepared by any suitable method known to one of ordinary skill in the art, for example by contacting glass fibers with a static or dynamic applicator, such as a roller or belt applicator, To the glass fiber. The total concentration of non-volatile components in the sizing composition can be adjusted over a wide range depending on the application means to be used, the nature of the glass fibers to be sized and the weight of the dried size coat desired for the intended use of the sized glass fiber. In some embodiments, the sizing composition can be applied to glass fibers during the forming operation of the fibers.

In another aspect, certain embodiments of the present invention relate to glass fiber strands. In some embodiments, the glass fiber strand comprises a plurality of glass fibers, wherein at least one of the plurality of glass fibers is at least partially coated with one of the sizing compositions disclosed herein. For example, some embodiments of fiberglass strands may include a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with one or more maleic anhydride copolymers, one or more coupling agents, and further an epoxy compound . In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 40% by weight of the sizing composition on a total solids basis. In some embodiments, the reaction product of the alkoxylated amine and polycarboxylic acid, which is further reacted with the epoxy compound, is present in an amount greater than about 70% by weight of the sizing composition based on total solids.

In some embodiments, the sizing composition for at least partially coating the fiber of the fiberglass strand may further comprise at least one polymer selected from the group consisting of polyester, polyvinyl alcohol, polyurethane, polyvinylpyrrolidone, fatty acid esters of polyethylene glycol, acrylic, wax, ≪ RTI ID = 0.0 > rosin < / RTI > or epoxide.

Some embodiments of the present invention relate to roving comprising a plurality of glass fiber strands of the present invention. The roving, in some embodiments, can be assembled by winding a plurality of strands in a single package using a roving winder. In another embodiment, the roving is such that the plurality of glass fiber strands are unwound from their respective packages (e.g., a forming package or direct draw package) without being wrapped in a single package and combined into a single lobe to be provided in another processing unit , And can be assembled at the time of use. For example, the roving may be provided in a tub containing thermoplastic resin, chopped, kneaded, or otherwise processed whether rolled into a roving package or assembled at the point of use. The fiberglass strand and roving may be continuous in some embodiments, and in other embodiments may be cut (e.g., chopped) prior to use. Thus, depending on the application, fiberglass strands and glass fiber rovings according to some embodiments of the present invention may have any desired length. In some embodiments, the glass fiber roving of the present invention includes the roving described in U. S. Patent Application Publication 2003/0172683 Al (the disclosure of which is incorporated herein by reference in its entirety) At least a portion of the glass fibers used is at least partially coated with the sizing composition disclosed herein.

The chopped glass fibers at least partially coated with the sizing composition of the present invention provided herein can have any desired length. In some embodiments, the chopped fiberglass may have a length of greater than about 3 mm. In another embodiment, the chopped glass fibers can have a length of about 50 mm or less. In some embodiments, the chopped fiberglass may have a length of about 25 mm or less. In some embodiments, the chopped fiberglass may have a length of greater than about 50 mm.

In another embodiment, the present invention relates to a glass fiber reinforced thermoplastic or thermosetting composite. In some embodiments, the glass fiber-reinforced thermoplastic or thermosetting composite comprises at least one glass fiber at least partially coated with one of the sizing compositions described herein, and a thermoplastic or thermosetting resin. For example, in some embodiments, the glass fiber reinforced composite comprises a reaction product of an alkoxylated amine and a polycarboxylic acid, which is reacted with at least one maleic anhydride copolymer, at least one coupling agent, and further with an epoxy compound At least one glass fiber at least partially coated with a sizing composition comprising a thermoplastic resin or a thermosetting resin.

In some embodiments, the sizing composition used to coat the glass fibers in the thermoplastic or thermosetting composite further comprises a polymer selected from the group consisting of polyester, polyvinyl alcohol, polyurethane, polyvinyl pyrrolidone, fatty acid esters of polyethylene glycol, acrylic, wax, ≪ / RTI > may include one or more additional components, including rosins or epoxides,

In some embodiments of the fiber reinforced thermoplastic or thermosetting composite, the glass fibers in the composite have an average aspect ratio of 50 or greater. The fiber-reinforced thermoplastic or thermosetting composite may, in some embodiments, comprise a plurality of glass fibers having an average aspect ratio of 100 or greater. In some embodiments, the fiber-reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of 200 or greater in some embodiments. In another embodiment, the fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of 500 or greater. The fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of 600 or greater in some embodiments. The fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of less than 1500 in some embodiments. In another embodiment, the fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of less than 1200. The fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of less than 1000 in some embodiments. In another embodiment, the fiber reinforced thermoplastic or thermosetting composite may comprise a plurality of glass fibers having an average aspect ratio of greater than 1500.

The thermoplastic or thermosetting composite according to some embodiments may comprise a plurality of glass fibers at least partially coated with the sizing composition of the present invention. In one embodiment, the plurality of glass fibers may be present in an amount of at least about 10% by weight of the thermoplastic or thermosetting composite. In another embodiment, the plurality of glass fibers may be present in an amount of at least about 20% by weight of the thermoplastic or thermosetting composite. In some embodiments, the plurality of glass fibers may be present in an amount of at least about 30 weight percent of the thermoplastic or thermosetting composite. In some embodiments, the plurality of glass fibers can be present in an amount of up to about 90% by weight of the thermoplastic or thermosetting composite. In another embodiment, the plurality of glass fibers can be present in an amount of up to about 80% by weight of the thermoplastic or thermosetting composite. In another embodiment, the plurality of glass fibers may be present in an amount of up to about 75% by weight of the thermoplastic or thermosetting composite. In some embodiments, the fiber-reinforced thermoplastic or thermosetting composite comprising the plurality of glass fibers may be in the form of a pellet.

The glass fibers coated with the sizing composition of the present invention can be combined with various thermoplastic resins to form a glass fiber reinforced thermoplastic composite product. Examples of thermoplastic materials that can be used include polyolefins, polyacetals, polyamides (nylons), polycarbonates, polystyrenes, styrene-acrylonitrile copolymers, acrylonitrile-butadiene styrene (ABS) copolymers, polyvinyl chloride Polyethylene terephthalate, polybutylene terephthalate, and blends of thermoplastic resins.

In one embodiment, the thermoplastic resin reinforced with the sized glass fibers is a polyamide resin such as polyamide 6,6; Polyamide 4,6; Polyamide 6,10; Polyamide 6,12; Polyamide 6T (polyhexamethylene terephthalamide) and polyamide 6I (polyhexamethylene isophthalamide) obtained by condensation polymerization of diamine and dicarboxylic acid; Polyamide 9T; Polyamide 6 and polyamide 12 obtained by ring-opening polymerization of lactam; polyamides 11 obtained by autocondensation of? -aminocarboxylic acids; ≪ / RTI > and copolymers and blends thereof. The specific polyamide resin can be selected based on the mechanical properties of the resin, the heat resistance, the crystallization temperature, the moldability and the appearance of the molding.

In some embodiments, the polyamide thermoplastic resin is selected from the group consisting of fatty acid metal salts such as capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, behenic acid, Sodium, lithium, calcium, magnesium, zinc or aluminum salts of fatty acids having at least 9 carbon atoms, such as sulfuric acid and erucic acid. In addition, two or more fatty acid metal salts may be used together. The fatty acid metal salt improves the mold releasing property of the resin by reducing the torque during melt-kneading the thermoplastic polyamide resin and the sized glass fiber in the extruder and improves the melt fluidity of the resin during injection molding . In one embodiment, calcium stearate is used to lubricate the polyamide resin to be reinforced with the sized glass fibers. As described in connection with the sizing composition of the present invention, caprolactam blocked isocyanates can improve the strength of the calcium stearate lubricated polyamide resin.

In some embodiments, additional additives may be incorporated into the fiber reinforced polyamide resin such as, but not limited to, stabilizers, flame retardants, fillers, and impact modifiers. Examples of additional additives that may be added in some embodiments include blends of one or more heat stabilizers such as copper iodide and potassium iodide, such as Polyad Preblend from Ciba Specialties, 201 (but not limited to). In some embodiments, the thermal stabilizer may include phenolic antioxidants, such as (without limitation) Irganox 1009 and Irganox 245 from Ciba Specialty Chemicals. In some embodiments, the impact modifier may include maleic anhydride grafted rubber, such as (without limitation) Exxelor VA 1803 from ExxonMobil.

Glass fibers coated with the sizing composition of the present invention can also be combined with a number of thermosetting resins to form glass fiber reinforced thermosetting composite products. In some embodiments, the thermosetting resin reinforced with the glass fiber of the present invention comprises a polyester resin, a polyimide resin, a phenol resin, a vinyl ester resin, or an epoxy resin.

In another aspect, certain embodiments of the present invention are directed to a method of making a glass fiber-reinforced thermoplastic or thermosetting composite. In some embodiments, a method of making a fiber-reinforced thermoplastic or thermosetting composite comprises providing a plurality of continuous phase glass fibers and at least partially coating the plurality of continuous phase glass fibers with any of the sizing compositions of the present invention , And placing a plurality of coated glass fibers in the thermoplastic resin. In one embodiment, a method of making a fiber-reinforced thermoplastic or thermosetting composite comprises providing a plurality of continuous phase glass fibers, wherein the plurality of continuous phase glass fibers is mixed with one or more maleic anhydride copolymers, And a sizing composition comprising a reaction product of an alkoxylated amine and a polycarboxylic acid that is further reacted with the epoxy compound, and positioning the plurality of glass fibers in the thermoplastic or thermosetting resin. In some embodiments, locating a plurality of sized glass fibers in a thermoplastic or thermosetting resin includes drawing a plurality of the sized glass fibers into a thermoplastic or thermosetting resin. In some embodiments, the liquid thermoplastic resin comprises a polyamide resin.

In some embodiments of the method of making a fiber-reinforced thermoplastic or thermosetting composite, the sizing composition further comprises at least one polymer selected from the group consisting of polyester, polyvinyl alcohol, polyurethane, polyvinylpyrrolidone, fatty acid esters of polyethylene glycol, acrylic, wax, ≪ / RTI > may include one or more additional components, including rosins or epoxides,

The method of making a fiber-reinforced thermoplastic or thermosetting composite according to some embodiments further comprises chopping the plurality of continuous phase glass fibers and the thermoplastic or thermosetting resin into a pellet. In another embodiment, the method of making a fiber-reinforced thermoplastic or thermosetting composite further comprises molding a plurality of continuous phase glass fibers and a thermoplastic or thermosetting resin.

In some embodiments, the method of making a fiber-reinforced thermoplastic composite includes G-LFT (Granular Long Fiber technique). In another embodiment, the method of making a fiber-reinforced thermoplastic composite comprises D-LFT (Direct-Long Fiber technique). In another embodiment, the method of making a fiber-reinforced composite comprises a C-LFT (continuous phase fiber technique) that allows the production of an impregnated tape.

In the G-LFT process, a long glass fiber granule or pellet is produced through a thermoplastic pearlitization process. The sizing composition of the present invention facilitates impregnation of the glass fibers with the polymer resin. The impregnated glass fibers are plasticized in a gentle manner in which damage or breakage of the fibers in the extruder is avoided. The granules or pellets are then formed into a desired shape of the shaped article by a compression molding or injection molding process. A long fiber granule or pellet impregnated with a polymer resin is provided as a semi-product and is usually produced at a location separate from the place where the granule or pellet is formed into a molded article by compression or injection molding techniques.

In the D-LFT process, since the kneading system and the forming system are integrated to provide a one-step long fiber-reinforced composite material from the raw material, a granular or pellet of glass fiber pre-impregnated with a polymer resin is provided as a semi-product The step is omitted. For example a continuous phase strand of glass fiber, into the extruder for kneading with the plasticized plastic resin in such a way that the length of the strand is not significantly reduced. Alternatively, chopped strands of glass fibers may be provided and introduced into an extruder for kneading with a plasticized polymeric resin. The heated compound is then fed in-line into a compression or injection molding apparatus for molding production.

Some illustrative embodiments of the invention are now illustrated in the following non-limiting specific embodiments.

Example 1: Sizing composition formulation (20L)

Sizing composition component Amount (g) Acetic acid (80% active in water) 24 Silane ¹ 72 Maleic anhydride copolymer ² 900 Reaction product ³ 3375 water Sheep made with 20L 1: DYNASYLAN AMEO, commercially available from Degussa AGE, Dusseldorf, Germany
2: Ammonia neutralized aqueous solution of an alternating copolymer of ethylene / MA- 20% active, ethylene and maleic anhydride (EMA of Zinc Chemical Chemicals, Inc.)
3: A mixture of phthalic anhydride and an alkoxylated primary amine (e. G., Trymeen), additionally reacted with bisphenol A diglycidyl ether (EPON 880 or EPON 828LS or EPIKOTE 880 from Hecion Specialty Chemicals) 6617), 20% active in water

The sizing composition of Example 1 was prepared by providing about 115 kg of demineralized water in a binder tank equipped with a stirrer. The amount of acetic acid as specified in the water in the binder tank was added and stirred for 5 minutes. After stirring, a specified amount of silane was added to the binder tank and the resulting solution was stirred for 10 minutes. After stirring for 10 minutes, a specified amount of maleic anhydride copolymer and the reaction product were added to the binder tank. The solution was made up to 20 L with additional demineralized water. The resulting sizing composition had a pH of 7.5.

The reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound, for use in the sizing composition of Example 1, was prepared as follows. The reaction mixture was prepared by mixing primary alkoxylated amine (Trifimin 6617) and polycarboxylic acid (phthalic anhydride) in a mixing ratio of 1: 2 in a mixing tank. The resulting reaction mixture was heated to 200 < 0 > C and held at 200 < 0 > C for 1 hour. CO ₂ was bubbled through the reaction during heating.

After 1 hour, the reaction mixture was cooled to 150 < 0 > C and an aromatic epoxy compound (EPON 880 or EPON 828LS or EPIKOTE 880, commercially available from Hecion Specialty Chemicals, Ohio, Columbus, Ohio) was added to the mixing tank The molar ratio of the alkoxylated amine to the aromatic epoxy compound was 1: 2. The resulting reaction mixture was heated to 200 < 0 > C over 10-15 minutes to produce a solid reaction product. The reaction product was dissolved in demineralized water to form a solution or dispersion of the reaction product.

The following Examples 2 to 5 may also be carried out according to the procedure described above, with maleic anhydride and other ingredients being added to the binder tank after the silane.

Example 2: Sizing composition formulation (20L)

Sizing composition component Amount (g) Acetic acid 24 Silane ⁴ 72 Maleic anhydride copolymer ⁵ 900 Reaction product ⁶ 1125 Additional Ingredients ⁷ 776 water Sheep made with 20L 4: commercially available from Degussa AGE, Degussa AG, Düsseldorf, Germany
5: Ammonia neutralized aqueous solution of an alternating copolymer of ethylene / MA-20% active, ethylene and maleic anhydride (EMA of Zinc Chems Inc.)
6: A mixture of phthalic anhydride and an alkoxylated primary amine (e.g., Tritium 6617), which was further reacted with bisphenol A diglycidyl ether (EPON 880 or EPON 828LS or EPIKOTE 880 from Hecion Specialty Chemicals) The reaction product, 20% active in water
7: Whitcomb W290H from Baxenden, 60% active in water

Example 3: Sizing composition formulation (20L)

Sizing composition component Amount (g) Acetic acid 24 Silane ⁸ 72 Maleic anhydride copolymer ⁹ 900 Reaction product ¹⁰ 1688 Additional ingredients ¹¹ 1688 water Sheep made with 20L 8: commercially available from Degussa AGE, Degussa AG, Düsseldorf, Germany
9: Ammonia neutralized aqueous solution of an alternating copolymer of ethylene and MA-water 20% active, ethylene and maleic anhydride (EMA of Zinc Chems Inc.)
10: A mixture of phthalic anhydride and an alkoxylated primary amine (e.g., Trifmine 6617), additionally reacted with bisphenol A diglycidyl ether (EPON 880 or EPON 828LS or EPIKOTE 880 from Hecion Specialty Chemicals) The reaction product, 20% active in water
11: mohiol-3-85 from Kuraray, 20% activity in water

Example 4: Sizing composition formulation (20L)

Sizing composition component Amount (g) Acetic acid 24 Silane ¹² 72 Maleic anhydride copolymer ¹³ 900 Polyurethane ¹⁴ 1164 water Sheep made with 20L 12: commercially available from Degussa AGE, Degussa AG, Düsseldorf, Germany
13: Ammonia neutralized aqueous solution of an alternating copolymer of ethylene / MA-20% active, ethylene and maleic anhydride (EMA of Zinc Chemis Inc.)
14: Whitcomb W290H from Becksenden, 20% active in water

Example 5: Sizing composition formulation (20L)

Sizing composition component Amount (g) Acetic acid 24 Silane ¹⁵ 72 Maleic anhydride copolymer ¹⁶ 900 The blocked isocyanate ¹⁷ 2077 water Sheep made with 20L 15: commercially available from Degussa AGE, Degussa AG, Düsseldorf, Germany
16: Ammonia neutralized aqueous solution of an alternating copolymer of ethylene / MA-20% active, ethylene and maleic anhydride (EMA of Zinc Chemicals, Inc.)
14: Rhodocoat WT-1000 from Rhodia, 33% active in water

A preferred characteristic that can be seen by the various (but not all) embodiments of the present invention is that the sizing composition which can advantageously maintain the strength of a glass fiber reinforced thermoplastic resin, for example a long fiber reinforced thermoplastic resin, offer; Providing sizing compositions that can facilitate processing long glass fibers with G-LFT (Granular Long Fiber technique), D-LFT (Direct Long Fiber technique) and / or C-LFT (Continuous Fiber technique) , And the like.

Various embodiments of the present invention are described herein. These embodiments are merely illustrative of one or more of the principles of the present invention. Those skilled in the art will readily be able to make various changes and modifications of the present invention without departing from the spirit and scope thereof.

Claims (44)

One or more maleic anhydride copolymers, One or more coupling agents, and The reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound A sizing composition for glass fibers, Wherein the reaction product is present in an amount greater than 40 weight percent of the sizing composition based on total solids. The method according to claim 1, Wherein the reaction product is present in an amount greater than 50 weight percent of the sizing composition based on total solids. The method according to claim 1, Wherein the reaction product is present in an amount greater than 70% by weight of the sizing composition based on total solids. The method according to claim 1, Wherein said at least one maleic anhydride copolymer comprises a maleic anhydride monomer and a monomer selected from the group consisting of ethylene, butadiene, isobutylene, and mixtures thereof. The method according to claim 1, Wherein said at least one maleic anhydride copolymer comprises a carboxylate moiety, a carboxylate salt moiety, an amide moiety, an imide moiety, or a combination thereof. 5. The method of claim 4, Wherein said at least one maleic anhydride copolymer is present in an amount less than 50 weight percent of the sizing composition based on total solids. 5. The method of claim 4, Wherein said at least one maleic anhydride copolymer is present in an amount of up to 40 weight percent of the sizing composition on a total solids basis. The method according to claim 1, Wherein the at least one coupling agent comprises silane. 9. The method of claim 8, Wherein the silane comprises an aminosilane. The method according to claim 1, Wherein said at least one coupling agent is present in an amount of up to 20 weight percent of the sizing composition on a total solids basis. The method according to claim 1, Wherein the at least one additional component is selected from the group consisting of polyesters, polyvinyl alcohols, polyurethanes, polyvinylpyrrolidones, fatty acid esters of polyethylene glycols, acrylic, waxes, chemically modified rosins, An epoxy, and an epoxy. The method according to claim 1, Wherein the alkoxylated amine comprises an alkoxylated aliphatic amine. 13. The method of claim 12, Wherein the alkoxylated aliphatic amine comprises an alkoxylated dodecylamine, an alkoxylated tetradecylamine, an alkoxylated hexadecylamine, an alkoxylated stearylamine, an alkoxylated octadecylamine, or a mixture thereof. Sizing composition for fibers. The method according to claim 1, Wherein the alkoxylated amine comprises an ethoxylated amine, a propoxylated amine, a butoxylated amine, or a mixture thereof. The method according to claim 1, Wherein the polycarboxylic acid comprises an aromatic polycarboxylic acid. 16. The method of claim 15, Wherein the aromatic polycarboxylic acid comprises phthalic acid, terephthalic acid, isophthalic acid or a mixture thereof. The method according to claim 1, Wherein the epoxy compound comprises a polyepoxy compound. 18. The method of claim 17, Wherein the polyepoxy compound comprises a diglycidyl ether, a diglycidyl ester, or a mixture thereof. 19. The method of claim 18, Wherein the diglycidyl ether comprises an alkyl diglycidyl ether, an aromatic diglycidyl ether, or a mixture thereof. 20. The method of claim 19, Wherein the aromatic diglycidyl ether comprises a bisphenol A diglycidyl ether. A glass fiber at least partially coated with the sizing composition of claim 1. 22. The method of claim 21, Wherein the glass fibers are continuous phase glass fibers. 22. The method of claim 21, Wherein the glass fibers are chopped glass fibers. 24. The method of claim 23, Wherein said chopped glass fibers have a length of at least 3 mm. 24. The method of claim 23, Wherein the chopped glass fiber has a length of 50 mm or less. 24. The method of claim 23, Wherein said chopped glass fibers have a length of greater than 50 mm. The polymeric resin and A plurality of glass fibers according to claim 21 ≪ / RTI > 28. The method of claim 27, Wherein the polymeric resin comprises a thermoplastic resin. 29. The method of claim 28, Wherein the thermoplastic resin is selected from the group consisting of polyolefins, polyacetals, polyamides, polycarbonates, polystyrenes, styrene-acrylonitrile copolymers, acrylonitrile-butadiene styrene (ABS) copolymers, polyvinyl chloride (PVC), polyethylene terephthalate ≪ / RTI > or a mixture thereof. 28. The method of claim 27, Wherein the polymer resin comprises a thermosetting resin. 31. The method of claim 30, Wherein the thermosetting resin comprises a polyester resin, a polyimide resin, a phenol resin, a vinyl ester resin, or an epoxy resin. 28. The method of claim 27, Wherein the plurality of glass fibers have an average aspect ratio of 50 or more. 28. The method of claim 27, Wherein the plurality of glass fibers have an average aspect ratio of 200 or more. 28. The method of claim 27, Wherein the plurality of glass fibers is present in an amount of at least 10 wt% of the composite. 28. The method of claim 27, Wherein the plurality of glass fibers is present in an amount of up to 90% by weight of the composite. Providing a plurality of continuous phase glass fibers, Wherein the plurality of continuous phase glass fibers are at least partially dispersed in a sizing composition comprising a reaction product of an alkoxylated amine and a polycarboxylic acid, wherein the reaction product is further reacted with at least one maleic anhydride copolymer, at least one coupling agent, Wherein the reaction product is present in an amount greater than 40 weight percent of the sizing composition based on total solids, Placing a plurality of coated continuous glass fibers in a polymeric resin ≪ / RTI > 37. The method of claim 36, Further comprising chopping the coated plurality of continuous phase glass fibers prior to placing the coated plurality of continuous phase glass fibers in the polymer resin. 37. The method of claim 36, Wherein the polymer resin comprises a thermoplastic resin. 39. The method of claim 38, Wherein the thermoplastic resin is selected from the group consisting of polyolefins, polyacetals, polyamides, polycarbonates, polystyrenes, styrene-acrylonitrile copolymers, acrylonitrile-butadiene styrene (ABS) copolymers, polyvinyl chloride (PVC), polyethylene terephthalate ≪ / RTI > or a mixture thereof. 37. The method of claim 36, Wherein the polymer resin comprises a thermosetting resin. 41. The method of claim 40, Wherein the thermosetting resin comprises a polyester resin, a polyimide resin, a phenol resin, a vinyl ester resin, or an epoxy resin. One or more maleic anhydride copolymers, One or more coupling agents, and The reaction product of an alkoxylated amide and a polycarboxylic acid, which is further reacted with an epoxy compound A sizing composition for glass fibers, Wherein the reaction product is present in an amount greater than 40 weight percent of the sizing composition based on total solids. One or more acrylic polymers, One or more coupling agents, and The reaction product of an alkoxylated amine and a polycarboxylic acid, which is further reacted with an epoxy compound A sizing composition for glass fibers, Wherein the reaction product is present in an amount greater than 40 weight percent of the sizing composition based on total solids. 44. The method of claim 43, Wherein the at least one acrylic polymer is polyacrylic acid, polymethacrylic acid, polymethyl methacrylate, or a combination thereof.